EP2755919B1 - Formulierung einer kolloidalen titanoxidlösungszusammensetzung für beschichtungs- und druckverfahren sowie verbesserung der ausgabeleistung und lebensdauer von organischen p-i-n/n-i-p-fotovoltakikzellen - Google Patents

Formulierung einer kolloidalen titanoxidlösungszusammensetzung für beschichtungs- und druckverfahren sowie verbesserung der ausgabeleistung und lebensdauer von organischen p-i-n/n-i-p-fotovoltakikzellen Download PDF

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EP2755919B1
EP2755919B1 EP12756745.1A EP12756745A EP2755919B1 EP 2755919 B1 EP2755919 B1 EP 2755919B1 EP 12756745 A EP12756745 A EP 12756745A EP 2755919 B1 EP2755919 B1 EP 2755919B1
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solvent
precursor
titanium oxide
colloidal solution
nanoparticles
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French (fr)
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EP2755919A1 (de
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Luc René Roger BROHAN
Arkadiusz Michal KARPINSKI
Mireille RICHARD-PLOUET
Solenn Berson
Stéphane GUILLEREZ
Mickaël BARRET
Jérôme MOURAO
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Ardeje
Centre National de la Recherche Scientifique CNRS
Universite de Nantes
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Ardeje
Centre National de la Recherche Scientifique CNRS
Commissariat a lEnergie Atomique CEA
Universite de Nantes
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/08—Drying; Calcining ; After treatment of titanium oxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of colloidal solution based on titanium oxide nanoparticles, and its implementation by printing, in particular by inkjet in the field of energy production from solar radiation.
  • the present invention relates in particular to a stable colloidal solution based on titanium oxide nanoparticles for the preparation of a semiconductor material making it possible in particular to improve the service life and / or the efficiency of energy conversion devices. based on such a material, and in particular on photovoltaic devices.
  • the present invention relates to the preparation of this colloidal solution, the preparation of semiconductor material, the preparation of solar energy conversion devices, as well as their uses.
  • the invention aims to improve the efficiency of energy conversion devices from solar radiation, and / or their lifespan.
  • the present invention also aims to reduce the cost of production of such devices.
  • nanoparticles of titanium oxide and in particular of amorphous titanium oxide or of titanium dioxide (crystallized in the form anatase).
  • These nanoparticles are generally prepared by sol-gel processes from titanium oxide precursors such as titanium (IV) isopropoxide (Ti [OCH (CH 3 ) 2 ] 4 ), orthotitanate tetra-butyl (Ti [C 4 H 9 O 4 ]), or a solution of titanium oxysulfate (TiOSO 4 at about 15% by weight in dilute sulfuric acid), see for example GB 2,473,712 A .
  • the solvents used differ according to the nature of the precursor: isopropyl alcohol or butanol in general.
  • Titanium complexing agents such as acetylacetone (CH 3 C (O) CH 2 C (O) CH 3 ) dispersed in 2-methoxyethanol (CH 3 OCH 2 CH 2 OH)., Or ethanolamine (H 2 NCH 2 CH 2 OH), or diethylamine ((CH 3 CH 2 ) 2 NH) are added to the solutions containing the titanium precursor.
  • the mixture is brought to reflux (approximately 80 ° C.) for a few hours (1-2 hours) and then deposited by centrifugal coating ("spin-coating") or electrodeposition on a transparent conductive substrate.
  • the deposited film undergoes a second heat treatment at 120-150 ° C or 450 ° C for 30 min to 1 hour, depending on the nature of the polymer or glass substrate. Annealing at low temperature leads to an amorphous form of TiO x while the second allows the crystallized variety anatase of TiO 2 to be obtained.
  • TiO x solutions prepared from alcoholic titanium oxide precursors are expensive, sensitive to atmosphere and water. In this sol-gel process, the hydrolysis and condensation mechanisms of titanium oxide are not controlled since they depend on the relative humidity and the temperature. The polycondensation kinetics of TiO x being very fast, it is practically impossible to obtain under these conditions solutions of crystallized nanoparticles having a low dispersion of particle sizes.
  • the compulsory annealing step constitutes a severe limitation, in particular in the context of the use of solar cells on polymer substrates.
  • the performance of organic cells depends closely on the nature of the species present on the surface of the nanoparticles and therefore on the amorphous or crystallized nature of titanium oxide. It is important to control the size, the crystallinity of the nanoparticles and the chemical composition of their surface.
  • the deposits of amorphous titanium oxide are produced by centrifugal coating (“spin-coating”), coating by immersion (“dip-coating”), or electrodeposition and no formulation of stable colloidal solution containing nanoparticles of titanium dioxide. is currently suitable for printing techniques.
  • colloidal solutions based on titanium oxide can be produced which are stable and usable for preparing devices for converting solar energy, in particular by printing.
  • the invention relates according to a first aspect to a process for the preparation of a colloidal solution of nanoparticles, characterized in that it comprises (a) the dissolution of a titanium oxide precursor known as “precursor” in one or more solvents called “precursor solvent”, and (b) chemical transformation, preferably by hydrolysis, of said precursor into titanium oxide and of said solvent of the precursor into a solvent of colloidal solution, to form nanoparticles of titanium oxide dispersed in the colloidal solution solvent, said colloidal solution having a dynamic viscosity of between 4 and 60 cP at 20 ° C and 101,325 Pa.
  • the precursor used for the present invention is advantageously an aqua-oxo titanium chloride ([Ti 8 O 12 (H 2 O) 24 ] Cl 8 , HCl, 7H 2 O).
  • a precursor can be prepared according to the process described in the international application WO 2004/101436 from TiOCl 2 (titanium aquo-oxo chloride, process for its preparation; L. Brohan, H. Sutrisno, E. Puzenat, A. Rouet, H. Terrisse. - French patent of CNRS N ° 0305619 ; the European patent application EP 04 742 604.4 ; the japanese patent JP2006-530327 , and the American patent US7858064 ).
  • titanium oxide precursor such as in particular TiOSO 4 , TiCl4 (in particular in aqueous medium), TiF4, TiOF2, a titanium alkoxide in acidic medium (acetic acid, H 2 SO 4 , HCI ).
  • the transformation of the titanium oxide precursor into titanium oxide is typically carried out by hydrolysis at low temperature (preferably at a temperature below 200 ° C., and generally between 20 and 200 ° C, more preferably between 50 and 180 ° C, for example 120 ° C) in the presence of at least water and propylene carbonate.
  • the solvents of the invention are chosen from solvents which allow good dispersion of the precursor and nucleation of titanium oxide nanoparticles. At least two solvents form the solvent for the titanium oxide precursor.
  • the "precursor solvent” comprises at least a first solvent and a second solvent, where the first solvent is consumed, in whole or in part, by the chemical transformation of the second solvent, and where the second solvent is converted, in whole or in part, preferably by hydrolysis, into a third solvent, said solvent of colloidal solution comprising at least the third solvent, and optionally the first and / or the second solvent.
  • the method of the invention comprises bringing the titanium oxide precursor into contact with a two-phase solvent (and preferably with one of the solvents of the two-phase solvent, the second solvent being added next) then the transformation of the two-phase solvent by hydrolysis (or self-hydrolysis if the two-phase solvent comprises water) into a single-phase solvent comprising nanoparticles of titanium oxide.
  • the first solvent is water, a solvent with a high dielectric constant. This solvent typically allows the precursor to dissolve before the nucleation phase.
  • the second solvent is advantageously chosen to control the nucleation and growth of the titanium oxide nanoparticles.
  • the reactor autoclave
  • the reactor autoclave
  • the reactor can be heated for a time and a temperature sufficient to transform the precursor of titanium oxide into titanium oxide, for example at a temperature between 80 and 150 ° C, for example 120 ° C, for 48 hours.
  • a variant of the process consists in operating under reflux, in particular to reduce the reaction time.
  • the crystals, previously dissolved in the first solvent, and the second solvent are added to the enclosure.
  • the mixture is heated for a time and temperature sufficient to transform the titanium oxide precursor into titanium oxide, preferably at a temperature between 80 and 150 ° C for 24 hours, with continuous stirring.
  • This variant of the process of the invention has the advantage of accessing stable colloidal solutions in shorter preparation times (24h instead of 48h).
  • the reaction can therefore be carried out in an autoclave or in a reactor fitted with a reflux device.
  • the second solvent is hydrolyzed in an acid medium to a third solvent to generate the solvent for the colloidal solution.
  • this hydrolysis is carried out during the hydrolysis of the titanium oxide precursor, as for example according to figure 1 .
  • the present invention is based in particular on the principle of modifying the properties of the solvent of the precursor (which may be a mixture of solvents) to generate a new system of one or more solvents (solvent of colloidal solution) in which the nanoparticles of titanium oxide formed are stable.
  • solvent of colloidal solution solvent of colloidal solution
  • stable is meant that the solution has 12 months after its preparation a dispersion of the particles comparable, and preferably substantially identical, to the initial colloidal solution.
  • the viscosity of the colloidal solution is controlled by stopping the chemical transformation step of the solvent of the precursor.
  • the adjustment of the concentration of the different reagents in particular: titanium oxide precursor, and hydrochloric acid used in particular for the hydrolysis of the titanium oxide precursor
  • the solvents or compounds forming the solution solvent precursor colloidal leads to the formation of a stable colloidal solution containing nanoparticles of titanium oxide, and in particular of titanium dioxide in the form of anatase.
  • the present invention advantageously makes it possible to control the kinetics of transformation of the titanium oxide precursor and of said solvent of the precursor in order to adjust the diameter and the size dispersion of the titanium oxide nanoparticles. It is sought to obtain nanoparticles whose particle size is not very dispersed, and preferably monodisperse, and preferably whose hydrodynamic diameter is at most 50 nm for non-agglomerated nanoparticles. Beyond 50 nm, the inventors have found that the properties of the colloidal solution are not sufficiently satisfactory for the applications envisaged, and in particular for using a printing technique, in particular by inkjet. Nanoparticles are preferred whose hydrodynamic diameter is centered around 5 to 10 nanometers with a minimum value of 2 nm and maximum of 30 nm, and preferably 25 nm.
  • the solvent of the precursor has a dynamic viscosity suitable for dissolving the titanium oxide precursor (generally between 1 and 3 cP), and the dynamic viscosity of the colloidal solution of nanoparticles after hydrolysis of the titanium oxide precursor is between 4 and 54 cP, and for example between 4 and 25 cP, or even between 8 and 15 cP, at 20 ° C and 101 325 Pa.
  • the viscosity measurement is typically carried out using an SV-10 viscometer Vibro-Viscosimeter (Codemes): Two gold plates are immersed in the sample; the amplitude of their vibration, calibrated in water, varies according to the viscosity of the fluid. The sample is placed in a glass tank on a thermostated support to carry out the measurements at 20 ° C, temperature at which the measurements of size and zeta potential were carried out.
  • the viscosity is particularly suitable for the use of the colloidal solution by printing, and in particular by inkjet printing.
  • the present invention advantageously allows viscosity control during the preparation of the colloidal titanium oxide solution.
  • the viscosity is advantageously controlled by the degree of progress of the reaction.
  • the viscosity is controlled by stopping the chemical transformation step of the solvent of the precursor.
  • This control is carried out in particular through the reaction conditions, and for example by the nature of the reagents used (precursor, solvent, or other) or their concentrations, the reaction temperature, the pressure, the time of reaction, the molar ratio between the reactants and / or solvents, or any combination of these parameters.
  • This control of the reaction makes it possible to adapt the viscosity of the formulation to the desired application.
  • this reaction is particularly advantageous for the preparation of semiconductors by printing.
  • the second solvent for the precursor is propylene carbonate.
  • an acid medium there is hydrolysis of propylene carbonate which is transformed into propane-diol and into carbonic acid.
  • propane-diol can optionally hydrolyze in fine to 2-chloro-propan-1-ol. This is particularly the case in the presence of hydrochloric acid.
  • the formation of the colloidal solution results from a double hydrolysis: that of the titanium oxide precursor and that of propylene carbonate.
  • the reaction product (propylene glycol) has a viscosity of 54 cP at room temperature. This difference offers the opportunity to formulate the solution with the desired viscosity by controlling the degree of progress of the reaction. It is therefore preferable to choose solvents which are hydrolysable or chemically transformable, the viscosity of which is significantly different before and after hydrolysis or chemical transformation.
  • the present invention advantageously makes it possible to change (increase or decrease, and preferably increase) the viscosity so as to initially dissolve the titanium oxide precursor, then to form stable titanium oxide nanoparticles in particular by the modification controlled viscosity of the solvent of the precursor.
  • the solvent of the precursor comprises water (first solvent), and propylene carbonate (PC) (second solvent), preferably with a molar ratio [water] / [PC] of between 0.1 and 1, 5, and preferably between 0.2 and 1.2, and more preferably between 0.5 and 0.8.
  • the solvent precursor of colloidal solution comprises water and propylene glycol.
  • the molar ratio [water] / [PG] is preferably between 0.1 and 1.5, and preferably between 0.1 and 0.7.
  • the hydrolysis temperature is preferably between 100 and 150 ° C.
  • the surface tension of the solvent of the precursor is preferably between 20 and 40 mN / m.
  • the hydrolysis time is preferably between 90 minutes and 70 hours, preferably between 8 and 60 hours, at a temperature of 120 ° C.
  • the concentration is expressed in grams of titanium for reasons of convenience.
  • the formulation of the colloidal solution for inkjet printing requires a precise adjustment of the viscosity, generally between 8 and 15 cP at the printing temperature, which can be controlled by a heating element inside the module. 'impression.
  • the present invention also makes it possible to control the pH of the colloidal solution of titanium oxide.
  • the pH of the colloidal solutions in order to prevent possible corrosion of the printing modules.
  • the pH thus controlled is also advantageous for protecting against corrosion of any other device brought into contact with the colloidal solution.
  • the titanium oxide precursor when the titanium oxide precursor is brought into contact with the solvent mixture (propylene carbonate-water) there is intermediate formation of 1,2 propane-diol (or propylene glycol) which, by nucleophilic exchange reaction, transforms into 2-chloro-1-propanol.
  • the solvent mixture propylene carbonate-water
  • 1,2 propane-diol or propylene glycol
  • three chemical reactions take place whose kinetics differ according to the initial and reaction conditions ( Figure 1 ).
  • the transformation of the titanium oxide precursor into titanium oxide produces hydrochloric acid
  • the hydrochloric acid produced is consumed by reaction with at least one compound of said solvent of colloidal solution or a compound formed during chemical transformation. solvent for the precursor.
  • the solvent of the precursor is added with a colloidal solution solvent, or a solvent forming part of the colloidal solution solvent. It is thus possible to add the third solvent defined above to the solvent of the precursor.
  • propylene glycol can be added to a water-propylene carbonate mixture. This makes it possible to significantly improve the rheological properties and to reduce the dispersity of the nanoparticles in the colloidal solution.
  • the colloidal solution of titanium oxide nanoparticles is exposed to UV rays to improve its absorption properties of solar radiation.
  • the invention relates in a second aspect to a colloidal solution of titanium oxide nanoparticles comprising a dispersion of titanium oxide nanoparticles in a solvent or solvent system whose viscosity is between 4 and 54 cP, at 20 ° C. and at 101,325 Pa, which is obtained by the inventive method.
  • the colloidal solution preferably comprises nanoparticles of titanium oxide in the form of anatase.
  • the previous methods do not make it possible to obtain stable colloidal solutions containing nanoparticles of crystallized titanium oxide (anatase). This is particularly the case of the method described in the international application WO 03/064324 (Sol-gel polymer based on titanium oxide).
  • the colloidal solution obtained comprises, depending on the initial titanium concentration and the aging time, nanoparticles of hydrodynamic diameter 1.5 nm, or two-dimensional polymer networks of titanium oxide.
  • Requirement WO 2004/101436 does not provide a stable solution or crystallized nanoparticles.
  • the present invention allows the preparation of a stable colloidal solution containing anatase nanoparticles, monocrystalline.
  • the nanoparticles of the invention preferably have a hydrodynamic diameter between 2 and 50 nm and the aggregates, if they are present, have preferably a hydrodynamic diameter between 50 and 250 nm, and preferably between 50 and 180 nm.
  • the colloidal solutions of the invention do not contain aggregates (or substantially not) or are eliminated.
  • the nanoparticles tend to agglomerate together and therefore to give rise to a population of particles which is not sufficiently monodisperse.
  • This agglomeration can be avoided by treating the colloidal solution of such nanoparticles by illumination under UV radiation.
  • this treatment consists in exposing the colloidal solution to UV radiation such as for example at a wavelength of 365 nm, for a time sufficient to eliminate any aggregates present. This duration is typically between 1 and 24 hours.
  • the invention therefore relates in particular to a colloidal solution of mono-dispersed nanoparticles.
  • the colloidal solution of the invention is capable of being obtained by any of the methods described above or below, including any combination of the variants or embodiments.
  • the solvent for the colloidal solution is advantageously obtained as described above.
  • this solvent is obtained by hydrolysis of the solvent for the titanium oxide precursor.
  • the colloidal solution of the invention especially forms a sol-gel material.
  • the colloidal solution of the invention comprises or consists of nanoparticles of titanium oxide and in particular of titanium dioxide in anatase form, dispersed in 2-chloro-1-propanol optionally comprising propylene glycol and / or the water.
  • the present invention relates, according to a third aspect, to the use of a colloidal solution as defined above, or capable of being obtained according to the method of the invention, for the preparation of an n-type semiconductor.
  • the invention also relates according to a fourth aspect to a process for the preparation of an n-type semiconductor layer comprising the preparation of a colloidal solution as defined above, and the deposition of a layer of colloidal solution on a substrate to form an n-type semiconductor layer comprising titanium oxide nanoparticles.
  • the deposition is preferably carried out by printing or coating, and more preferably by centrifugal coating ("spin coating”), printing by ink jet, by screen printing, screen printing, and / or by the unwinding process. with contact (“Roll-to-roll”), possibly using one or more patterns on the substrate (“patterning”).
  • spin coating centrifugal coating
  • patterning possibly using one or more patterns on the substrate.
  • inkjet printing makes it possible to produce a directly structured layer corresponding to the desired design and the parameters associated with the process to control the characteristics of the layers produced (thickness, underlying layer, etc.). This process also makes it possible to minimize the loss of materials in the implementation.
  • the process may include deposition in solution on a substrate followed by annealing at a temperature between 50 and 500 ° C, preferably between 50 and 200 ° C.
  • a colloidal solution as described above is deposited on a transparent conductive or semiconductor substrate.
  • the invention relates according to a fifth aspect to a photovoltaic device comprising an n-type semiconductor material capable of being obtained according to the methods described above.
  • This device is typically a photovoltaic cell of PIN or NIP type, an organic transistor, or a light-emitting diode.
  • the invention relates in particular to an organic photovoltaic cell.
  • the invention relates according to a sixth aspect to a method of manufacturing a photovoltaic device comprising the deposition on a substrate of the colloidal solution (in typical form of sol-gel material).
  • the layer of material n can be annealed between 50 and 200 ° C. Its thickness is for example between 10 and 200 nm.
  • the active layer of the photovoltaic device is then generally deposited on the layer of material n.
  • a temperature treatment between 50 and 180 ° C for 0 to 30 minutes often allows optimization of the morphology of the active layer.
  • a p-type interfacial layer is then generally deposited on the active layer. Heat treatment at a temperature typically between 50 and 180 ° C from 0 to 30 minutes usually allows the performance of the device to be optimized.
  • An electrode is then typically deposited by the liquid route or by vacuum evaporation on the P-type layer.
  • the active layer is generally composed of an n-type semiconductor material (fullerenes, fullerene derivatives, perylene, n-type semiconductor polymers, etc.) mixed with a p-type semiconductor material (P3HT, polythiophene and its derivatives, copolymers of polythiophene or polycarbazole, etc.).
  • n-type semiconductor material fullerene derivatives, perylene, n-type semiconductor polymers, etc.
  • P3HT p-type semiconductor material
  • polythiophene and its derivatives copolymers of polythiophene or polycarbazole, etc.
  • the p-type interfacial layer generally comprises a p-type conductive polymer (PEDOT: PSS, doped polythiophenes, etc.) or semiconductor metal oxide (V 2 O 5 , MoO 3 NiO, WO 3 ).
  • PEDOT p-type conductive polymer
  • semiconductor metal oxide V 2 O 5 , MoO 3 NiO, WO 3
  • the titanium oxide layer is produced by inkjet printing using a printing platform integrating modules printing generating drops from 1 to 100pL (picoliters).
  • the printing strategies are adapted in order to obtain homogeneous layers of targeted thickness.
  • the concentration of titanium oxide in the colloidal solution used is adapted as a function of the printing strategy.
  • the thermal annealing optionally applied is preferably similar to that used for the layers produced by coating.
  • the n layer is used on a conductive or semi-conductive surface for organic or hybrid photovoltaic device, photodiode (as for sensor applications), or light-emitting diode for conductive or semiconductor surfaces.
  • colloidal solutions of the invention are stable and compatible with printing techniques.
  • the use of the colloidal solutions of the invention makes it possible to increase the life of photovoltaic devices.
  • the lifespan is typically at least 6,500 hours with a yield loss of less than 15%.
  • the yields (conversion into PCE power - in English "Power Conversion Efficiency") of the photovoltaic device of the present invention are typically from 2 to 5%.
  • the present invention also relates to a method of producing energy comprising the use of an n-type semiconductor material capable of being obtained according to the methods described above, or of a photovoltaic device, as defined previously, to produce energy, and in particular electricity, from solar radiation.
  • the synthesis of colloidal solutions is based on the transformation of the precursor [Ti 8 O 12 (H 2 O) 24 ] Cl 8 • HCl • 7H 2 O into TiO 2 nanoparticles.
  • the reaction is carried out at low temperature (120 ° C) in the presence of a binary mixture of solvents consisting of propylene carbonate and water.
  • the selected solvents allow good dispersion of the precursor and nucleation of TiO 2 nanoparticles.
  • the use of the solvent with a high dielectric constant (water) allows the precursor to dissolve before the nucleation phase.
  • Propylene carbonate cyclic ester
  • the viscosity of the formulation of the colloidal solution for the envisaged applications, and in particular for inkjet printing, can be adjusted precisely, for example to obtain a viscosity of between 8 and 15cP at the printing temperature ( temperature of the print nozzles, generally between 20 and 80 ° C) and at atmospheric pressure.
  • the hydrolysis kinetics of the propylene carbonate-acid water mixture strongly depends on their initial proportion.
  • the figure 2 and Table 1 show the evolution of the final viscosity of the colloidal solutions as a function of the water / propylene carbonate molar ratio, after 48 hours of reaction at 120 ° C.
  • the hydrolysis of propylene carbonate to 1,2 propane-diol is manifested by the disappearance of the mode of vibration associated with the carbonyl group at 1780 cm -1 and by the appearance of the mode of vibration of OH at 3400cm -1 due to the formation of 1,2 propane-diol. In all cases, the vibration mode at 1650 cm -1 attributable to the presence of water is absent.
  • the dotted line represents the theoretical conversion rate and the curves of medium, fine thickness, and significant the conversion rate for the values 0.09g, 0.18g and 0.27g of [Ti 8 O 12 (H 2 O) 24 ] Cl 8 • HCl • 7H 2 O, respectively.
  • the mass and molar values of the reagents as well as those of the viscosity of the colloidal solutions are collated in Table 3.
  • Table 3 Initial chemical composition of the reagents and viscosity of colloidal solutions. No.
  • the reaction time in the autoclave is also a determining factor in the progress of the hydrolysis of propylene carbonate.
  • the samples are autoclaved at 120 ° C for variable times.
  • the conductivity which is proportional to the concentration of the ions, decreases continuously from 0.24mS / cm measured after 2 hours to 0.0094mS / cm after 64 hours of autoclave treatment.
  • the low conductivity values measured after 15 hours of heat treatment reveal that almost all of the H + and Cl - ions are consumed.
  • Example 4 Diameter of the nanoparticles and aggregates
  • the size of the nanoparticles and agglomerates contained in the colloidal solutions of different concentrations was measured by photon correlation spectroscopy, 5 months after the synthesis.
  • the diameter of the nanoparticles and aggregates as a function of the initial formulation of the colloidal solutions is reported on the figure 10 .
  • Colloidal solutions are easily diluted in an alcoholic medium (Images of transmission electron microcopy, figure 11 , where the colloidal solution is diluted 100 times in ethanol, after illumination under UV for 12 hours) and contain nanoparticles of TiO 2 anatase (X-ray diffraction diagram figure 12 for a powder obtained by drying the colloidal solution at 70 ° C).
  • the figure 24 shows the distribution by PCS (Photon Correlation Spectroscopy or in English "Photon Correlation Spectroscopy”) of the size (hydrodynamic diameter) of the particles of colloidal solution No. 9 before illumination under UV, which is centered on 5 nm. It can be seen that the minimum particle size is 2.2 nm and the maximum size around 32 nm. The absence of Gaussian distribution results from the physical limit of detection of particles with hydrodynamic diameter less than 1 nm.
  • PCS Photon Correlation Spectroscopy or in English "Photon Correlation Spectroscopy
  • Example 5 Improvement of the quality of the colloidal solutions by addition of Propylene glycol.
  • Propylene glycol is a product of the hydrolysis of propylene carbonate.
  • the addition of propylene glycol to the initial propylene carbonate / water composition significantly improves the rheological properties and the mono-dispersity of the colloidal solutions.
  • the formulations of the colloidal solutions explored are collated in Table 4.
  • the viscosities are between 5 and 25 cP values which frame the range of interest for inkjet printing technology.
  • solutions containing only one population are mono-dispersed ( Figure 13 , with solutions N ° 19 to 22).
  • N ° 8 and N ° 12 are respectively transparent (particle diameter ⁇ 20nm) and slightly opaque (particle diameter ⁇ 100nm), after exposure under UV overnight then contact with air solution N ° 12 becomes transparent with an average particle diameter of approximately 50nm. Similar behavior is observed for all samples. This phenomenon results from redox reactions which occur, under UV illumination, at the nanoparticle interface of titanium oxide / adsorbate. The red coloration would be attributable to the formation of peroxo species in the presence of oxygen while the blue color results from the formation of Ti3 +.
  • colloidal solutions of TiOx / TiO 2 can be prepared using the precursor [Ti 8 O 12 (H 2 O) 24 ] Cl 8 • HCl • 7H 2 O and the water / propylene glycol (PG) mixture as solvent.
  • the synthesis is carried out in an autoclave at 120 ° C for 48 hours.
  • Example 8 Applications to organic photovoltaic cells of the PIN and PIN type
  • Colloidal solutions based on titanium oxide are used for producing the n-type semiconductor thin layer.
  • Example 9 Processes for producing the inter-facial layer n
  • the colloidal solution of the invention is deposited on a transparent conductive or semiconductor substrate.
  • the deposition methods used can be chosen from spin coating, coating / spreading (Dr Blade, "strip casting"), methods printing (inkjet, screen printing, gravure printing, ...), etc. It is also possible to use a patterning of the substrate.
  • the TiO x layer is produced by inkjet printing using a printing platform integrating printing modules generating drops from 1 pL to 100 pL (pL: pico -liter).
  • the printing strategies are adapted in order to obtain homogeneous layers of targeted thickness, as well as the TiO x concentration of the formulation used.
  • the thermal annealing applied is similar to that used for the layers produced by coating.
  • the n layer according to the invention is used on a conductive or semi-conductive surface of organic or hybrid solar cells, photodiodes (sensor application), light-emitting diodes.
  • the photovoltaic cells prepared comprise a glass or plastic substrate (PET, PEN), covered with a layer of ITO which is itself covered with a semiconductor oxide n TiO x This is covered with an active film composed of a P3HT / PCBM mixture.
  • the active layer is successively coated with a layer of PEDOT: PSS or other p-type doped semiconductor material (HTL Hole Transporting Layer) and then with a silver anode.
  • the configuration of the cell is therefore as follows: substrate / ITO / TiOx / polymer + PCBM / PEDOT: PSS or other HTL / Ag.
  • Step 1 A layer of TiO x is produced from a precursor solution by spinning deposition (Solution No. 9 after UV illumination for 12 h ). The duration of the coating is 60 s at 1000 rpm-1 then 30 s at 2000 rpm. The thickness of the layer obtained is about 50 nm, the deposition is carried out in air, then dried on a hot plate at 150 ° C. for 1 hour.
  • Step 2 The active layer is deposited by spinning a P3HT / PCBM composition, on the n layer, at around 1500 rpm for 40 s then 2000 rpm for 35 s.
  • Step 3 A layer of HTL (approximately 50 nm) is deposited with the spinner at 2000 rpm for 25 s then 3000 rpm for 25 s.
  • Step 4 A silver electrode (100 nm) is then evaporated under vacuum.
  • the cells are then characterized in a glove box under a controlled atmosphere.
  • the current-voltage characteristics (I (V)) are recorded on a Keithley® SMU 2400 device under AM1.5 lighting at a power of 1000 W.m.
  • Table 6 summarizes the photovoltaic conversion yields of the devices produced.
  • the insertion of the TiO x layer increases the lifetime of the cell and increases its efficiency with a loss of less than 15% over 6500h.
  • TiO x 1 solution N ° 9 without UV illumination
  • TiO x 2 solution No. 9 after UV illumination for 12 hours (blue solution)
  • TiO x 3 after UV illumination for 1 hour (orange-red solution)

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Claims (21)

  1. Verfahren zur Herstellung einer kolloidalen Lösung von Nanopartikeln des Titanoxids, dadurch gekennzeichnet, dass es umfasst (a) das Lösen eines Vorläufers des Titanoxids, genannt "Vorläufer", in einem Lösungsmittel des Vorläufers, wobei das Lösungsmittel mindestens Wasser und Propylenkarbonat (PC) umfasst, wobei der Vorläufer des Titanoxids ausgewählt ist aus Titan-aquo-oxo-chlorid, TiOSO4, TiCl4, TiF4, TiOF4 und Titanalkoxid in saurem Medium und (b) die chemische Transformation durch Hydrolyse des Vorläufers in Titanoxid und des Propylenkarbonats in ein Lösungsmittel der kolloidalen Lösung, wobei das Wasser insgesamt oder teilweise durch die chemische Transformation des Propylenkarbonats verbraucht wird, und das Propylenkarbonat insgesamt oder teilweise durch Hydrolyse in ein drittes Lösungsmittel transformiert wird, um Nanopartikel des Titanoxids zu bilden, die in dem Lösungsmittel der kolloidalen Lösung verteilt sind, das mindestens das dritte Lösungsmittel und gegebenenfalls Wasser und Propylenkarbonat enthält, wobei die kolloidale Lösung eine dynamische Viskosität zwischen 4 und 54 cP bei 20°C und 101 325 Pa aufweist, wobei die Viskosität durch Anhalten des Schrittes der chemischen Transformation des Lösungsmittels des Vorläufers gesteuert wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die dynamische Viskosität der kolloidalen Lösung von Nanopartikeln zwischen 4 und 25 cP bei 20°C und 101 325 Pa liegt.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die dynamische Viskosität der kolloidalen Lösung von Nanopartikeln zwischen 8 und 15cP bei 20°C und 101 325 Pa liegt.
  4. Verfahren nach einem beliebigen der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es das Inkontaktbringen des Vorläufers des Titanoxids mit einem zweiphasigen Lösungsmittel, das mindestens Wasser und Propylenkarbonat enthält, und dann die Transformation des zweiphasigen Lösungsmittels durch Hydrolyse in ein einphasiges Lösungsmittel, das die Nanopartikel des Titanoxids umfasst.
  5. Verfahren nach einem beliebigen der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Verfahren die Hydrolyse des Propylenkarbonats in Kohlensäure und Propandiol umfasst.
  6. Verfahren nach einem beliebigen der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Propandiol in 2-chloro-propan-1-ol in Anwesenheit von Salzsäure hydrolysiert wird.
  7. Verfahren nach einem beliebigen der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Lösungsmittel des Vorläufers ein Molverhältnis [Wasser]/[PC] zwischen 0,1 und 1,5, vorzugsweise zwischen 0,2 und 1,2 und noch bevorzugter zwischen 0,5 und 0,8 aufweist.
  8. Verfahren nach einem beliebigen der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Konzentration des Vorläufers, ausgedrückt in Konzentration an Titan, zwischen 0,005 und 0,1 M.L-1 liegt.
  9. Verfahren nach einem beliebigen der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Transformation des Vorläufers in Titanoxid Salzsäure erzeugt und dass die erzeugte Salzsäure durch Reaktion mit mindestens einer Verbindung des Lösungsmittels des Vorläufers oder einer Verbindung, die während der chemischen Transformation des Lösungsmittels des Vorläufers gebildet wird, verbraucht wird.
  10. Verfahren nach einem beliebigen der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass dem Lösungsmittel des Vorläufers Lösungsmittel der kolloidalen Lösung oder ein Lösungsmittel, das Teil des kolloidalen Lösungsmittels ist, hinzugefügt wird.
  11. Verfahren nach einem beliebigen der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die kolloidale Lösung von Nanopartikeln des Titanoxids einer UV Strahlung ausgesetzt wird, um ihre Eigenschaften der Absorption der Sonnenstrahlung zu verbessern.
  12. Kolloidale Lösung von Nanopartikeln des Titanoxids, dadurch gekennzeichnet, dass sie durch ein Verfahren nach einem beliebigen der Ansprüche 1 bis 10 erhalten wird.
  13. Kolloidale Lösung nach Anspruch 12, dadurch gekennzeichnet, dass sie Nanopartikel des Anatas-Titanoxids und die vorzugsweise einen hydrodynamischen Durchmesser der Nanopartikel zwischen 2 und 50nm aufweisen, und Anhäufungen enthält, die, wenn sie vorhanden sind, vorzugsweise einen hydrodynamischen Durchmesser zwischen 50 und 250 nm und vorzugsweise zwischen 50 und 180 nm aufweisen.
  14. Verwendung einer kolloidalen Lösung, wie sie nach einem beliebigen der Ansprüche 12 bis 13 definiert ist, oder die geeignet ist, nach einem Verfahren, wie es nach einem beliebigen der Ansprüche 1 bis 11 definiert ist, erhalten zu werden, für die Herstellung eines Halbleiters des n-Typs.
  15. Verfahren zur Herstellung einer Halbleiterschicht des n-Typs, dadurch gekennzeichnet, dass es die Herstellung einer kolloidalen Lösung, wie sie nach einem beliebigen der Ansprüche 12 bis 13 definiert ist, oder die geeignet ist, nach einem Verfahren, wie es nach einem beliebigen der Ansprüche 1 bis 11 definiert ist, erhalten zu werden, und die Ablagerung durch Aufdrucken einer Schicht der kolloidalen Lösung auf ein Substrat umfasst, um eine Halbleiterschicht des n-Typs zu bilden, die Nanopartikel des Titanoxids enthält.
  16. Verfahren nach Anspruch 15, dadurch gekennzeichnet, dass die Ablagerung durch Aufdrucken und vorzugsweise durch Aufdrucken mit einem Tintenstrahl durchgeführt wird.
  17. Verfahren nach Anspruch 15 oder 16, dadurch gekennzeichnet, dass es die Ablagerung der kolloidalen Lösung auf einem Substrat, gefolgt von einem Glühen bei einer Temperatur zwischen 50 und 500°C umfasst.
  18. Photovoltaische Vorrichtung, dadurch gekennzeichnet, dass sie ein Halbleitermaterial des n-Typs enthält, das geeignet ist, nach einem beliebigen der Ansprüche 15 bis 17 erhalten zu werden.
  19. Photovoltaische Vorrichtung nach Anspruch 18, dadurch gekennzeichnet, dass sie eine photovoltaische Zelle des Typs PIN oder NIP, einen organischen Transistor oder eine Lumineszenzdiode darstellt.
  20. Verfahren zur Herstellung einer photovoltaischen Vorrichtung, dadurch gekennzeichnet, dass es die Herstellung einer Halbleiterschicht des n-Typs, wie sie nach einem beliebigen der Ansprüche 15 bis 17 definiert ist, umfasst.
  21. Verfahren zur Energieerzeugung, dadurch gekennzeichnet, dass es die Verwendung des Halbleitermaterials des n-Typs, das geeignet ist, nach einem beliebigen der Ansprüche 15 bis 17 erhalten zu werden, oder eine photovoltaischen Vorrichtung, wie sie nach den Ansprüchen 18 oder 19 definiert ist, zur Erzeugung von Energie aus Sonnenstrahlung umfasst.
EP12756745.1A 2011-09-16 2012-09-12 Formulierung einer kolloidalen titanoxidlösungszusammensetzung für beschichtungs- und druckverfahren sowie verbesserung der ausgabeleistung und lebensdauer von organischen p-i-n/n-i-p-fotovoltakikzellen Active EP2755919B1 (de)

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